HU190582B

HU190582B - Agricultural and horticultural fungicide and nematocide compositions containing n,n-disubstituted azole-carbox-amide derivatives and process for producing these compounds

Info

Publication number: HU190582B
Application number: HU83733A
Authority: HU
Inventors: Hiroshi Yoshida; Kengo Koike; Shizou Shimano; Taizo Nakagawa; Kaora Ohmori
Original assignee: Nippon Kayaku Kabushiki Kaisha,Jp
Priority date: 1982-03-04
Filing date: 1983-03-03
Publication date: 1986-09-29
Also published as: DK84383D0; CS153183A2; ES520293A0; CS241520B2; AU1161583A; AU553831B2; CA1194485A; EP0088380A2; DK84383A; ES8500269A1; EP0088380B1; US4500536A; DE3367592D1; IL67975A; EP0088380A3; BR8300971A

Abstract

Disclosed herein are novel derivatives of N,N-substituted, azolecarboxamide represented by the formula (I) : wherein R₁ represents a hydrogen atom, methyl group, ethyl group or propyl group; R₂ represents an alkyl group of 1 to 6 carbon atoms; R₃ represents a hydrogen atom or methyl group; A represents a hydrogen atom or methyl group; X and Y represent a carbon atom or a nitrogen atom respectively, provided that when X represents a nitrogen atom, Y represents a nitrogen atom or carbon atom and when X represents a carbon atom, Y represents a nitrogen atom; and Z represents an oxygen atom or sulfur atom, provided that when Z represents a sulfur atom, A represents only a hydrogen atom; and an agricultural or horticultural fungicidal or nematicidal composition containing the novel derivative of the formula (I) as an active ingredient.

Description

Patent: (73)

Níppon Kayuku Kabushiki Kaisha, Tokyo, (54) NN — DISTRIBUTED AZOL — EUNGICID AND NATOCIDES USED IN AGRICULTURE AND HORTICULTURE INCLUDING CARBOX AMID.

PREPARATIONS AND PROCEDURES FOR COMPOUNDS (57) EXTRACT

The compositions of the present invention comprise N, N-disubstituted azole carboxamide derivatives of the formula I wherein R 1 is hydrogen, methyl, ethyl or propyl;

R 2 is C 1-6 alkyl;

R3 is hydrogen or methyl;

A is hydrogen or methyl;

X and Y are independently CH or nitrogen, with the proviso that when X is nitrogen then Y is nitrogen or CH and when X is CH then Y is nitrogen and

Z is O or S, provided that when Z is S, then A is H alone.

Field of the Invention The present invention relates to a nematocide and fungicide composition for use in agriculture and garden cultures comprising a derivative of N, N-disubstituted azole carboxamide, and a method for preparing the active ingredient.

The novel derivatives of the Ν, Ν-substituted azole carboxamide of the present invention can be represented by the formula (II) wherein

II Ri is hydrogen, methyl, ethyl or propyl; R2 C 1-6 alkyl; R3 is hydrogen or methyl; THE is hydrogen or methyl; X and Y is independently CH or N, provided that when X is N, Y is N or CH and when X is CH then Y is N and Z is an oxygen or sulfur atom, provided that when Z is sulfur, then A is exclusively hydrogen.

However, organic chlorine compounds, organic sulfur compounds and gaseous compounds are known and used as fungicides to protect agricultural and horticultural crops from disease. However, organic chlorine compounds have the disadvantage that they are phytotoxic to cereal crops and often remain in plant parts and soils due to the high concentrations applied, as efficacy is low at lower concentrations. The disadvantage of organic sulfur compounds is that they often have phytotoxic effects on cereal crops and, in the case of direct contact, the operator may cause dermatitis. Furthermore, the disadvantage of gas-based compounds is that they have irritating and unpleasant odors. As the nematocide, so-called incense materials can be used. However, the drawback of the incense is that they often have phytotoxic effects on cereal plants and are irritating or unpleasant, and are not suitable for use directly on the nails.

It has been found that the novel compounds of formula (I) are highly effective against cereal diseases, nematodes such as fusaric wilting, powdery mildew, scab, gray mold, rice scorching, staring rice rice, barnu spotted rice nerve, Verticillium spinning, yellowing, rotting, citrus storage disease, seed disease, white rice nematodes, chrysanthemum leaf nematode, root knot nematodes, nematode damage, cyst nematodes, pine tree nematodes, without having known and used fungicides, bactericides, and nematocides with disadvantageous features and, moreover, unexpectedly are very effective against cereal diseases such as powdery mildew, gray mold, scab, etc. by applying to the soil where the cereal plant grows without having a detrimental effect, such as a phytotoxic effect on cereal crops, the inventors have thus accomplished the object of the present invention.

Although the use of certain azole carboxamide derivatives as fungicides is already known, for example, 50-31047. (1975) and 53-130668. (1978), these compounds are effective against the foliage of the plant against powdery mildew and other infections, but by treating the soil with the active ingredient in water, the known azole carboxamide derivatives are not effective. These derivatives have a weak systemic effect, i.e., having little penetration and translocation through the roots of the cultivated plant.

By contrast, the compounds of the present invention exhibit a high degree of anti-disease effect when applied to both the foliage of the cultivated plant and the soil as an aqueous solution. For example, to combat the infection of cucumber powdery mildew, which attacks the parts of the plant in the air above the soil, the aqueous compositions of the present invention are successfully used to soak the soil. The aqueous formulations of the present invention are also effective in impregnating the soil against Verticillium-induced wilting and soil-borne infections.

One of the characteristic features of the compounds of the present invention is that they have a systemic effect on the entire plant through its roots.

The compounds of the invention are prepared according to process (a) or (ib) as follows.

According to process variant (a), the carbamoyl halides of formula (II) are reacted with compounds of formula (III), preferably in an inert solvent, at a temperature in the range of 50 to 150 ° C for 10 minutes or a few hours. In formulas (II) and (III), R1, R2, R3, A, X, and Y are as defined above and Hal is halogen.

The hydrogen halide that develops during the reaction is bound by tertiary amines such as triethylamine or pyridine or excess azole compounds of formula (III).

According to process variant (b), the carbonyl-bis-azole compound of formula (VI) is reacted with a secondary amine of formula (V), preferably in the presence of an inert solvent, at a temperature of between 50 and 150 ° C for 10 minutes or several hours. over a period of time. In formulas (IV) and (V), R 1, R 2, R 5, A, X and Y are as defined above.

Suitable solvents for processes (a) and (b) include aromatic or aliphatic hydrocarbons or chlorinated aromatic and aliphatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, dichloromethane, 1.1. , 1-trichloromethane, chloroform, carbon tetrachloride and the like, or ethers such as diethyl ether, dioxane and tetrahydrofuran.

Furthermore, the carbamoyl halide of formula (II) can be prepared by the reaction of a secondary amine of formula (V) with the carbonyl halides of formula (VI) or (VII), preferably in an inert solvent at a temperature in the range of 0 to 150 ° C, min. or for a few hours.

In formulas (VI) and (VII), Hal is as defined above.

The carbonyl-bis-azole compounds of formula (IV) may be prepared by reacting an azo compound of formula (III) with a carbonyl halide of formula (VI) or (VII) in a preferred solvent, at a temperature range of 0 to 100 ° C. and 10 minutes and a few hours. Suitable acid scavengers include tertiary amines such as triethylamine and pyridine.

Among the carbonyl halides of formula (VI), the preferred phosgene and compounds of formula (VII) are trichloromethyl chloroformate. The azole compounds of formula (III), such as imidazole, pyrazole and triazole, may be prepared according to methods known in the art. Furthermore, the secondary amines of formula (V) can be prepared by reacting a halocarboxylic acid ester of formula (VIII), wherein R1, R2 are as defined above and Hal is halogen, with an amine of formula (IX): A and Z are as defined above.

In formula I, R2 is C1-C6 alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, amyl and hexyl.

Compounds of the present invention prepared according to the methods described above are summarized in Table I below.

Table I

Ν, Ν-disubstituted azole carboxamide derivatives

Compound number Ri R2 Ra XY Z THE Melting point or refractive index Appearance 1 H C2H5 H CH N 0 H Op: 35-37 C pale yellow crystals 2 CH3 -C2115 H CH N 0 H soi 1.51 ii brownish-yellow oily substance 3 CH3 C2H5 H N CH 0 H n »- ⁵ 1.51-11 light yellow oily substance 4 H C2H5 H N \ t 0 H so-called 1.5144 light yellow oily substance 5 CH3 C2H5 H NN 0 H πιι ^Λ 1.51 i-1 light yellow oily substance 6 CH3 -C4II9 (n) H CH N HE H n ,, »1.51 11 pale yellow oily substance 7 CH3 CH3 H CH N HE H Arrows- 'í.3} Π yellow oily substance 8 C2H5 CH3 II CH N 0 H Op: 69-71 ^U C pale yellow crystals 9 C2H5 -C3H7 (i) H CH N 0 H Op: 52-53 pale yellow

k crystals

Compound number Ri RZ R3 X Y Z THE Melting point or refractive index Appearance 10 Cha -C3H7 (n) H CH N 0 H 11- ⁵ 1.51 11 light yellow oily substance 11 Cha -C3H7 (i) H CH N 0 H M.p .: 88-89 ° C pale yellow crystals 12 H CH3 H CH N 0 H M.p .: 62-64 ° C pale yellow crystals 13 H -C3H7 (i) H CH N 0 H ni) - '1.51 11 light yellow oily substance 14 H -C4H9 (n) H CH N 0 H ni / ⁵ 1.51 il light yellow oily substance 15 CH3 -C4H9 (i) H CH N 0 H un-; ' 1.51 il light yellow oily substance 16 -CHs -C4H9 (chair) H CH N 0 H un- '1.5i 1 i light yellow oily substance 17 -CHs -C5H11 (n) H CH N 0 H Hl.- '1.5 in light yellow oily substance 18 CH3 -C5H11 (i) H CH N 0 H 'in-' 1.5 iii light yellow oily substance 19 CH3 —CeHia (ni H CH N 0 H ni / ⁵ (..>! 1 1. light yellow oily substance 20 H Cha H CH N s H M.p .: 69-72 ° C yellow crystals 21 H C2H5 H CH N s H M.p .: 64-66 ° C pale yellow crystals 22 H -C3H7 (i) H CH N s H ni / ⁵ 1.5 1 il light yellow oily substance 23 Cha CH3 H CH N s H l.iA.- light yellow oily substance 24 CH3 C2H5 H CH N s H what- 1.5! ·; ! light yellow oily substance 25 C2H5 C2H5 H CH N s H 111 / · '1: 11! 1 light yellow oily substance 26 C2H5 -C3H7 (i) H CH N s H ni / ⁵ - i light yellow oily substance 27 CH3 C2H5 Cha CH N s H brown oily substance 28 CH3 C2H5 H CH N 0 -CH3: behold ^2S 1.51 ii yellow oily substance 29 CH3 CH3 H CH N 0 -CH3 ii> - ^s I..51 í · ' yellow oily substance 30 -C3H7 (n) -C2H5 Cha CH N 0 H ni · - '.'1 yellow oily substance

Preferred compounds of the formula I are those in which R 1 is methyl or ethyl, R 5 and A are hydrogen, X is CH and Y is nitrogen. Particularly preferred are compounds wherein R 1 is methyl or ethyl R 8 and A is hydrogen, X is CH, Y is nitrogen, and Z is oxygen. Most preferred are compounds of formulas (Ia), (ld), (le), (If), (Ig), and (Ih).

The following examples illustrate the present invention without limiting our claims to the following:

Example 1

Preparation of (- (1 - / e toxocarbonyl-ethyl-N-furfuryl-imidazole-1-carboxamide using method b) Compound 12) Trichloromethyl ester of chloroformate (0.05 mol, 0.05 mol) was dissolved in anhydrous tetrahydrofuran (ml) and then dropwise at 0 to 10 ° C

13.6 g (0.2 mole) of imidazole and 10.1 g (0.1 mole) of triethylamine in 100 ml of anhydrous THF. The solution was then stirred for one hour and then a solution of N- (1-ethoxycarbonyl-ethyl) -N-furfurylamine (19.7 g, 0.1 mol) in dry tetrahydrofuran (40 ml) was added dropwise while maintaining the temperature. 5 to 10 ° C. The mixture thus obtained was heated under reflux for one hour and the cooled reaction mixture was poured into water and extracted with ethyl acetate. The extract was washed with water, then the washed extract was separated in the usual manner, dewatered and concentrated, and finally purified by silica gel chromatography. This gave 16 g (0.055 mol) of an oily product.

Using the same procedure as described above for 6 hours instead of refluxing for one hour at 50 ° C, the same oily product is obtained. Also, when o-dichlorobenzene is used instead of tetrahydrofuran and the reaction is refluxed instead of reflux for 1 hour. ^u It is carried out at C for 4 hours and is also obtained in the desired oily products. The physical constants of compound 2 thus prepared are as follows: Infrared absorption spectrum (KBr):

V (cnr ¹ )

1700 IC = O stretch, absorption of amide) and

1740 (C = 0 stretch, absorption of ester).

Magnetic Resonance Spectrum (CDCb): δ (ppm)

7.9 (ε, 1H, and 7.4 (d, 2H): proton sign of the imidazole ring

7.0 (s, 1H) and 6.35 (s, 2H): proton of the furan ring.

Example 2

To prepare N- (ethoxycarbonylmethyl) -N-furfuryltriazole-1-carboxamide using method (a) (Compound 4), trichloromethyl ester of chloroformate (0.05 mol) was dissolved in 100 ml. A solution of N- (1-ethoxycarbonylmethyl) -N-furfuramine (13 g, 0.071 mol) in dry tetrahydrofuran (100 ml) was slowly added dropwise in anhydrous tetrahydrofuran, while the reaction mixture was cooled to 0-5 ° C. After stirring for 30 minutes at room temperature, a solution of 9.8 g (0.121 mol) of triazole in dry tetrahydrofuran (200 ml) was added at 10-15 ° C. The reaction mixture was then gradually heated to reflux and kept under reflux for 1 hour. When the reaction was complete, the reaction mixture was cooled to room temperature and poured into water. The mixture was extracted with ethyl acetate, the extracts were washed with water as usual, separated, dehydrated and concentrated. The concentrate was chronographed on a silica gel column. In this way, 13 g (0.0468 mol) of an oily product (Compound 4) were obtained having the following physical constants:

Infrared Absorption Spectrum (KBr): (cnr ¹ )

1700 (C = 0 stretch, amide absorption) and

1740 (C = O stretching, absorption of ester)

Magnetic Resonance Spectrum (CDCl3): δ (ppm)

8.9 (s, 1H) and 7.95 (s, 1H): triazole ring proton

7.4 (s, 1H) and 6.4 (d, 2H): sign of the furan-like proton.

Example 3

N- (1- / e-toxocarbonyl-ethyl) -N- Preparation of 2-thienylmethyl) imidazole-1-carboxamide <24th To a solution of imidazole (6.8 g, 0.1 mol) in tetrahydrofuran (100 mL) was added trichloromethyl ester of chloroformate (5.0 g, 0.025 mol) while the solution was cooled to 0-10 ° C. Trielylamine (5.1 g, 0.05 mol) was added and the mixture was stirred at room temperature for 1 hour. To the reaction mixture was added N- (2-thienylmethyl) aniline (10.7 g, 0.05 mole) ethyl ester and stirred for 2 hours under reflux. The reaction mixture was then cooled to room temperature and poured into water. Its blends. the extract was washed with water in the usual manner, separated, dehydrated and concentrated and purified by column chromatography over silica gel. 10.8 g (0.035 mol) of an oily product were obtained. The physical constants of the carboxamide produced are: Infrared Absorption Spectrum (KBr):

V (cm ¹ )

1700 (C = O stretching, absorption of amide) and

1740 (C = 0 stretch, absorption of ester)

Magnetic Resonance Spectrum (CDCb): i (ppm)

8.0 (s, 1H): imidazole ring (1H) proton sign

7.4 (m, 2H): proton of imidazole ring (1H) is a proton signal of the thiophene ring (1H)

7.1 (m, 3H): the proton of the imidazole ring (1H) is the proton sign of the thiophene ring (2H).

Example 4

Preparation of N- (1- / ethoxycarbonyl-ethyl) -N- 1 - (2-thienyl) ethyl) imidazole-1-carboxamide (Compound 27) g (0.04 mol) of chlorine 4.3 g (0.054 mole) of pyridine were slowly added dropwise to a solution of trichloromethyl ester in 50 mL of toluene while maintaining the temperature of the solution under cooling with ice water at 0-10 ° C, then 10.5 g (0.046 mol) of N Ethyl ester of (1- (2-thienyl) ethyl) alanine was added to the mixture. After stirring for 2 hours at room temperature, a solution of imidazole (17 g, 0.25 mol) in tetrahydrofuran (80 ml) was added and the reaction mixture was refluxed for 3 hours. It was then cooled to room temperature, poured into water and extracted with ethyl acetate. The extract was washed with water in the usual manner, separated, dehydrated and concentrated, and finally purified by chromatography on a silica gel column. 5.2 g (0.016 mol) of an oily product were obtained.

If the aforementioned process was treated with 50 ° C for 8 hours instead of reflux for 3 hours, the same product was obtained. Similarly, when tetrafuran is replaced by o-dichlorobenzene and the reaction is carried out at 150 ° C instead of reflux for 3 hours, the desired product is also obtained. The physical constants of compound 27 thus prepared are as follows:

Infrared Absorption Spectrum (KBr): 0 (c.r. ¹ )

1690 (C = O elongation, absorption of amide)

1730 (C = 0 elongation, absorption of ester)

Magnetic Resonance Spectrum (CDCb): δ (ppm)

7.8 (s, 1H): sign of the imidazole ring (1H) proton

7.25 (m, 2H): the imidazole ring (III) proton sign is the proton signal of the thiophene ring (1H)

6.9 (m, 3H): The proton of the imidazole ring (1H) is the proton sign of the thiophene ring (2H).

1. Intermedier Production Example:

Preparation of N- (1-ethoxycarbonyl-ethyl) -furfurylamine

18.1 g (0.1 mol) of methyl-bromopropionate were added dropwise to furfurylamine cooled to 10-20 ° C with ice water (19.4 (0.2 mol)). The reaction mixture was stirred at room temperature overnight, then poured into water, and the oily substance thus formed was extracted with 100 mL of ethyl acetate. The ethyl acetate solution was then washed with water and dried over anhydrous sodium sulfate. The dried ethyl acetate solution was distilled under vacuum to give 16.2 g (0.082 mol) of an oily product. The product thus obtained is a colorless, transparent liquid having a boiling point of 3.85 ² Under reduced pressure:

120-125 ° C.

2. Intermediate production example

Preparation of N- (2-thienylmethyl) -alanine niethyl ester

Methyl α-bromopropionate (25 g, 0.15 mol) was added to 2-thienylmethylamine (17.0 g, 0.15 mol) and triethylamine (15.2 g, 0.15 mol) was added dropwise. ^u To a reaction mixture having a temperature of less than C. After stirring overnight, water (100 mL) was added and the resulting oily layer was extracted with ethyl acetate (100 mL). The extract was then separated, dried, concentrated, and the resulting concentrate was reduced to pressure breast, β d, s; tilláltuk. 24.0 g (0.12 mol) of a pale yellow oily product were obtained. ² Pa at reduced pressure: 98-103 ° C.

When the compounds of the invention are used as a fungicide or nematocide, the compounds may also be used in the form of compositions such as powders, microgranules, granules, etc.

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In the form of wettable powders, fluid formulations, emulsifiable concentrates and the like. These formulations may be prepared by conventional methods in the field of agrochemicals, but at least one Vision aid may be incorporated to promote or stabilize the efficacy of the composition.

These formulations can be applied directly to the ground in their original form or diluted with water to achieve the desired concentration.

Suitable excipients include carriers (diluents) and other enhancers, such as adhesives, emulsifiers, wetting, dispersing, fixing and disintegrating agents.

Liquid carriers include aromatic hydrocarbons such as toluene, xylene, or alcohols such as methanol, butanol, glycol or ketones such as acetone, or amides such as dimethylformamide, or sulfoxides such as dimethylsulfoxide, or others such as methylnaphthalene, cyclohexene, animal and vegetable oils, fatty acids, esters of fatty acids can be used.

Examples of solid carriers include clay, kaolin, talc, diatomaceous earth, silicon oxide, calcium carbonate montmorillonite, bentonite, feldspar, alumina and sawdust.

Typically, emulsifying and dispersing agents include surfactants, such as anionic surfactants such as sodium salts of high carbon sulphates, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl, lauryl betaine, or cationic surfactants. as well as nonionic surfactants and amphoteric surfactants. Additionally, for example, a polyoxyethylene nonylphenyl ether or a polyoxyethylene lauryl ether, such as polyoxyethylene nonylphenyl ether or dialkyl sulfosuccinate, may be used as a tackifier. Among the fasteners, carboxymethylcellulose or polyvinyl alcohol and disintegrants include sodium lignin sulfonate or sodium lauryl sulfate.

Formulations containing the compound of the invention as the active ingredient may be used not only alone, but may also be used in admixture with other fungicides, insecticides, plant growth regulators, miticides, herbicides, soil fungicides, soil improvers or nematocides, and may be used in combination with manure.

The fungicidal and nematocidal compositions comprising the compound of the present invention depend on the form and shape of the composition used, the method of application and other conditions in the agricultural and horticultural crops, the active ingredient content being generally from 0.5 to 95% by weight, preferably from 2 to 70% by weight.

The fungicidal or nematocidal compositions suitable for agricultural and horticultural purposes of the present invention are applied either on the leaves of the crop plant or on the soil where the plant is grown, and have excellent control effect on cereal plant diseases, especially in diseases that are above the soil of the cereal plant. such as powdery mildew, fungal fever, and gray mold directly in the soil. Furthermore, the nematocidal compositions of the present invention have significant nematocidal activity against rice white nematodes, chrysanthemum leaf nematodes, root knot nematodes, injured nematodes, nematode cysts, pine tree nematodes, and accordingly can be effectively used to kill these nematodes.

In practical applications, it is advantageous for these compositions to be dispersed so that the active ingredient concentration on the leaves and stems is 10-4000 ppm and, for soil application, 0.05-10 kg / 10 hectares.

The use of fungicidal or nematocidal compositions suitable for agricultural or horticultural purposes according to the invention is illustrated by the following examples, in which case the proportions and forms of active compound mixtures are not limited to the examples and may vary widely. In the examples, part.

1. Formulation example

Powder N- (1-ethoxycarbonyl-methyl) -N- (2-furfuryl) imidazole-1-carboxamide (Compound No. 1) 41 parts talc and 49 parts clay are mixed, followed by powder and powder. form.

2. Formulation example

Wettable powder portion N- (1- / ethoxycarbonyl) ethyl N- (2-furfuryl (imidazole-1-carboxamide (Compound No. 2), 15 parts kaolin, 3 parts high alcohol sulfate sodium) its salt and 2 parts of sodium polyacrylate are mixed and pulverized to form a wettable powder formulation.

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3. Formulation example

Granules include N- (1-ethoxycarbonyl-ethyl) -N- (2-5-furfuryl) -triazole-1-carboxamide (Compound No. 5), 35 parts diatomaceous earth, 23 parts bentonite, 37 parts talc and 2 parts of sodium lignin sulfonate are mixed and 18 parts of water are added to the mixture, so that the components 10 are uniformly wetted, then the mixture is loaded into an extrusion machine. The resulting granules were dried and dried to yield 0.6-1 mm granules. 15

4. Formulation example

Microgranules 20 parts of N- (1-ethoxycarbonyl-ethyl) -N- (2-furfuryl) -pyrazole-1-carboxamide (Compound No. 3), 6 parts of bentonite and 9 parts of clay are uniformly mixed together. The resulting mixture was pulverized to a thick powder, 80 parts of a 105-74 nm coarse, non-absorbent mineral powder were added separately to a suitable mixer, and until the mixer turned 20 parts of water was added to the mixer, and after the mineral powder was uniformly wetted, The dense powder formulation prepared above is added to the mixer, whereby the dense powder formulation will coat the mineral to form a microgranulate.

5. Formulation example

Emulsion Part N- (1-ethoxycarbonyl-ethyl) -N- (2-furfuryl) -imidazole-1-carboxamide (Compound No. 2) was dissolved in 63 parts xylene at 45 and 17 parts of 8: 2 alkylphenyl ethylene oxide condensate, a calcium alkylbenzene sulfonate mixture was added to give an emulsion.

6. Formulation example

Ultra Low Volume IU.LV) Mass Compound 2 Compound, i.e., N- (1- (ethoxycarbamoyl) -ethyl) -N- (2-furfuryl) imidazole-1-carboxarnidoL is mixed with 5 parts by weight of liquid paraffin.

The following experimental examples illustrate the excellent efficacy of the compounds of the invention against infections and nematodes in agricultural and horticultural crops:

1. Experimental example

Examination of control of cucumber powdery mildew

As described in Formulation Example 5, emulsions were prepared in place of Compound No. 2 using Compounds No. 7, 11, 21, 24-28, and 29, and the emulsion was diluted with water to provide an active ingredient content of 250. be in ppm and then planted in pots with cucumber seedlings (version: Kyozyoku green fushinari, in a leafy condition). After suppression, the cucumber plants were inoculated with Sphaerotheca fuliginea spore suspension, then the potted plants were stored in a greenhouse for two weeks, then examined for infection rate and infection index. The control value was calculated using the following formula. As a positive control, 70% thiophanate-methyl wettable powder (active ingredient: 1,2-bis (3-methoxycarbonyl) -2-thioureido) benzene] was used with water diluted to a concentration of 350 ppm of active ingredient.

(3 x A) + (2 X Β) + (1 x Cl

Infection Index = --—- χ ιθθ

X (A + B + C + D) where A: number of plants with severe infection symptoms

B: number of plants with significant levels of infection

C: The number of plants with low levels of infection

D: Number of plants without infection.

From the infection index thus recorded, the control values for each fungicide sample were calculated based on the following relationship:

Infection index in the untreated area

Control value =

Infection index in treated area ------ X 100 (Infection index in untreated area)

The test results are shown in Figure II. The table below is summarized.

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II. table

Test results for cucumber powdery mildew control

Test compound Concentration (ppm) Control value Fito toxicity No. 2 250 100 no No. 7 250 100 no 8.sz. 250 100 no 9.sz. 250 100 no 10.sz. 250 100 no No 11 250 100 no No 21 250 60 no 24.sz. 250 55 no 25.sz. 250 80 no 26.sz. 250 100 no 27.sz. 250 100 no 28.sz. 250 60 no No. 29 250 55 no control * 350 40 no

Note: Control: 70% thiophanate-methyl wettable powder.

2. Experimental example

Examination of cow control

As described in Formulation Example 5, an emulsion was prepared using compounds 11, 16, 23, 25, 26 or 27, and diluted with water to give an active ingredient content of 500 ppm. The emulsion formulation was used on cucumber plants planted in pots (version: Tokiwa jibai, single-leaf condition).

After susceptibility, cucumber strains were infected by sputtering with Cladosporiuni cucumerinum spore suspension, then the implanted pots were stored in a wet chamber at 20 ° C for one day and transferred to a greenhouse. The degree of infection on plants was tested 7 days after infection, and control values were calculated using the formula described in Experimental Example 1.

The test results are shown in Figure III. The table below is summarized.

III. table

Test results for cow control

Test compound Concentration (ppm) Control value Fito toxicity No. 2 500 80 no No 11 500 85 no 16.sz. 500 80 no 23.sz. 500 75 no 25.sz. 500 70 no 26.sz. 500 85 no 27.sz. 500 85 no untreated - 0

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3. Experimental Example

Examination of the control of botanical beans and grains

As described in Formulation Example 5, an emulsion was prepared as described in Examples 11, 16, 18, 22, 24,

Using the compounds of SEQ ID NOS: 26 and 27, replacing Compound No. 2 described in Example 5 and diluting with water to contain 500 ppm of active ingredient. The emulsion thus prepared was used on the shoots of a plant bean plant planted in pots (version: Shin-edogawa, in a leaf condition).

Diameter of injury in the untreated area

Control value = (Damage diameter a

After drying using a 5 mm diameter borehole, pieces were cut out of the cultured Botrytis cinerea myceria culture and placed on the primary leaf of the test plant, and the plants were placed in a wet chamber for infection, and the diameter of the primary leaf injury was checked for each compound after 48 hours of infection. and the control values were calculated based on the following relationship.

Diameter of injury in each treated area

--x ioo unmounted area)

The test results are shown in Figure IV. The table below is summarized.

ARC. table

Test results of anti-botanical control of gray bean

Test compound Concentration (ppm) Control value phytotoxicity No. 2 500 100 no No 18 500 90 no 22.sz. 500 70 no 24.sz. 500 70 no 26.sz. 500 80 no 27.sz. 500 85 no

4, Experimental Example

Investigation of cucumber-rotting protection In a cm-diameter unglazed tile we planted field soil and spread 5 g of contaminated soil on top of each soil, in which we cultivated Rhizoctonia solani culture, thus uniformly infecting the arable soil. Seeds of cucumber were sown in pots with infected soil, namely 10 seeds per pot (version: Ky Kyotooku green fushinari). As described in Formulation Example 5, emulsions were prepared as described in Figs. or 11, replacing Compound No. 2 described in Example 5 and diluted with water, then pouring 50 ml of diluted solutions into each well, and placing the soaked pots in a greenhouse. As control, 80% captan wettable powder (active ingredient: N- / trichloromethylthio / 50-tetrahydrophthalimide) was diluted with water at the same concentration as the test preparation. 10 days after seeding, we examined the condition of the infection and the percentage of healthy seedlings was calculated on the basis of the following 55 dependencies.

Number of healthy seedlings

Percentage of healthy seedlings in each area ------ _- I00

Number of healthy seedlings in untreated non-infected areas

The results of the study are summarized in Table V.

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Table V

Test results for cucumber rot control

Test compound Amount of compound per pot (g: active ingredient) Percentage of healthy seedlings phytotoxicity No. 2 0:05 85.0 no No.6 0:05 80.0 no 9.sz. 0:05 80.0 no loess. 0:05 85.0 no No 11 0:05 80.0 no control * 0:05 75.0 no control - 14.2 -

Note *: 80% Captane Wettable Powder.

5. Experimental Example

Examination of the control of cucumber powdery mildew in soil treatment

Cucumber sprouts (variant Tokiwa jibai, in a leafy state) were grown in pots placed in 10 cm diameter pots and then soaked with a diluted solution of the emulsions prepared as described in Formulation Example 5. Compounds 7-11, 22-26 or 27 were used to prepare the emulsions.

Example 5 instead of Compound # 2. The dosage amount is 25 ml per pot (i.e., 0.02525 g per tile for each active ingredient). As a control, N- (ethoxycarbonylmethyl) -N- (4-chlorophenyl) imidazole-1-carboxamide or dimethirimol (5-butyl-2-dimethylamino-6-methylpyrimidine-425) -ol) 12.5% liquid formulation was used. 3 days after soil treatment, the seedlings were infected with Sphaerotheca fuliginea spore suspension and the pots were stored in a greenhouse for 2 weeks. Thereafter, the rate of infection on the shoots was examined and the control value was calculated for each active ingredient based on the relationship described in Experimental Example 1. The results are shown in Figure VI. The table below is summarized.

VI. table

Test results for cucumber powder mildew in soil treatment

Test compound Amount of compound per pot (g: active ingredient) Control value phytotoxicity No. 2 0.0125 100 no No. 7 0.0125 150 no 8.sz. 0.0125 90 no 9.sz. 0.0125 50 no loess. 0.0125 50 no No 11 0.0125 90 no 12.sz. 0.0125 55 no 14.sz. 0.0125 50 no 19 th century 0.0125 80 no 20.sz. 0.0125 55 no 22.sz. 0.0125 55 no 23.sz. 0.0125 60 no 24.ez. 0.0125 70 no 25.sz. 0.0125 55 no No. 26 0.0125 100 no 27.sz. 0.0125 100 no 30.sz. 0.0125 95 no 1. Control 0.0125 5 no 2. Control 0.0125 50 no untreated - 0 -

-1 123

Note: 1. Control: N- (ethoxycarbonylmethyl) -N- (4-chlorophenyl-1-imidazole-1-carboxamide 31047 (1975), 12.5% liquid preparation

2. Control: DinieLirimol, 12.5% liquid preparation.

6. Experimental Example

Investigation of the control of cucumber rot in soil treatment

The wettable powder as described in Formulation Example 2 was prepared using Compound No. 7 instead of Compound No. 2 as described in Example 2. The solutions diluted with water were applied on the soil of cucumber flakes (variant Tokiwa jibai, in a leafy condition) grown in 10 cm diameter pots. The amount of dosing was 25 ml per pot. Cladosporlum cucurnerinum spore suspension was sprayed on the seedlings 1 day after soil treatment, and seedlings were placed in a humid chamber at 20 ° C for 1 day. The seedlings were then transferred to a greenhouse to expedite the development of the infection. The extent of infection was tested 7 days after challenge and the control values for each drug were calculated based on the relationship described in Experimental Example 1. The results are shown in Table VII. The table below is summarized.

VII. table

The amount of Compound A tested Control value per pot (g: active ingredient)

phytotoxicity

No. 2 0:03 100 no No. 2 0015 100 no No. 7 0:03 80 no No. 7 0015 60 no untreated - 0 -

7. Experimental Example

Examination of control of cucumber-gray mold

As described in Formulation Example 5, an emulsion was prepared using Compound No. 7 instead of Compound No. 2 described in Example 5 and diluted with water. Diluted solutions were poured onto cucumber seedlings (version: Fi Kyoryoku green fushinari, single leaf) planted in 10 cm diameter pots per 25 ml pots! quantities. From a culture of Botrytis cineria myceria in a Petri dish, 5 mm diameters were cut with a cork drill and placed on the first leaf of pa40 fungi. The potted seedlings were stored in a wet chamber to accelerate the development of the infection. 48 hours after infection, we examined the diameter of the injury in the vicinity of the myceria piece and the control values were calculated based on the correlation described in Experimental Example 3.

The results are shown in Table VIII. The table below is summarized.

VIII. table

Test compound

Amount of compound per pot (g: active ingredient)

Control value Phytotoxicity

s. 0:03 100 no s. 0015 100 no s. 0:03 85 no s* 0015 75 niiics

untreated

-1 225

8. Experimental Example

Examination of the control of cucumber fusarium

Field soil was placed in 12 cm unglazed pots, and then 15 g of contaminated soil, Fusarium oxysporum f. sp. Soil containing cucumerin culture was scattered to infect arable soil in pots. Then we poured cucumbers (version: Kvoryoku green fushinari) into pots, 10 seeds per pot. According to Formulation Example 5, using the compound of SEQ ID NO: 2, an emulsion was prepared with Lys, then diluted with water, and the diluted emulsion was used on pots grown in pots, in 50 ml portions per pot. Potted plants were stored in a greenhouse and 50% benomyl wettable powder was used as a control. 10 days after sowing, we examined the extent of infection and calculated the percentage of healthy seedlings using the relationship given in Experimental Example 4. The results are shown in Figure IX. The table below is summarized.

IX. table

Test compound Amount of compound per pot (g: active ingredient) Percentage of healthy seedlings phytotoxicity No. 2 0025 85 no control 0025 50 no untreated 0

Note: Control: 50% benomyl wettable powder formulation.

9. Experimental Example

Examination of the control of infection of citrus fruit by infection

Oranges were introduced into the emulsion prepared and diluted with water as described in Formulation Example 5. Fruits were dried and violated with a test specimen, and Penicillium italicum spore suspension was injected into the damaged fruit, then the fruit was placed in a wet chamber to infect.

As a control, 70% thiophanate-methyl wettable powder was used. I: 1,2-bis (3-methoxycarbonyl-2-thioureido) -benzene | The fungicidal effect was determined from the area of the lesions on the fruit. The results <0 is summarized in Table X.

Table X.

Test compound Concentration Percentage of damaged area phytotoxicity No. 2 500 0 no control 1000 10 no untreated - 90 -

Note: Control: 70% thiophanate-methyl wettable powder formulation.

10. Experimental Example

In vitro test for fungal activity

Using potato-agar medium, agar plate dilution method 1, 2, 3

Agar plates containing compounds of Formula 5 at a predetermined concentration were prepared and all of the compounds of Fig. XI were prepared. The pathogenic fungus in Table I was grown on agar plates so prepared. The fungi were cultured for 2.5 days at 2.5 ° C and the min 60 mole growth inhibitory concentration (MIC) for each compound was determined by the known method.

The results are shown in Figure XI. The table below is summarized.

-1 327

XI. table

MIC unit: microgram / ml

mushroom varieties E.g. Test compounds No. 2 No. 3 No. 5 Penicillium italicum 20 1 > 500 100 Pythium aphanidermatum > 500 > 500 500 500 Pyricularia oryzae 100 20 100 20 Helminthosporium oryzae 500 20 > 500 500 Botrytis cinerea 500 20 > 500 > 500 Verticillium albo-atrum 100 4 > 500 100

The XI. The numerical values given in Table 1 are shown 11. Experimental Example (MIC) micrograms / ml values. Less than 50 values show strong antifungal activity between 50 and 250 values 20 In vitro activity against fungal activity it has strong antifungal activity and 250-500 ta values between mid-antifungal activity meaning. The test described in Experimental Example 10 was carried out but as a pathogenic fungus 25 Verticillium albino was used and the test compounds were compounds 2, 6, 7 and 8. The results are shown in XII. The table below is summarized. XII. table

Test compounds MIC (microgram / ml) No. 2 4 No.6 20 No. 7 20 8.sz. 20 '

12. Experimental Example Infection Index = Examination of Verticillium-induced Wilting on Turkish Paradise According to Formulation Example 5, (4 x A) + (3 x B) + (2 x C) D ..... ,, - ▼ 1 45 4 x (A + B + C + D + E) instead of Compound No. 11, 21, 23, 24-26. or the use of a compound of \ t where the: number of plants where more than two-thirds of the leaves are damaged emulsions prepared with water were diluted with water and 50 was observed poured into 50 ml pots with Turkish tomato (version: Senryo No 2, five or six leaves) B: the number of plants where half or two thirds of lesions were observed condition). Then Verticillium C: azama with plants albo-atrum spore suspension was injected into the stem of the turkey tomato plants to infuse 55 one third of the leaves and one half of the lesions were injured to infect the plant. The infection index was determined 10 days after infection. Infection Index and Control Values a D: azama plants with less than 1/3 of the leaves being damaged based on the following relationship. As a positive control, 50% benomyl wettable powder was used (active ingredient: methyl / N-butylcarbamoyl-2-benzimidazole arm). 60 E: the number of plants where no damage was detected.

-1 429

Infection Index Infection index in the untreated area in the treated area

Control value = —-------------- X ΙθΟ (Infection index in untreated area)

The results are shown in Figure XIII. The table below is summarized.

XIII. t / íblázat

Test results of protection against verticillium-induced wilting on Turkish tomato plants

Test compound Amount of compound per pot (g: active ingredient) Control value Fito toxicity No. 2 0:02 100 no No. 11 0:02 100 no 13th century 0:02 95 no 15.sz. 0:02 100 no 17.sz. 0:02 100 no No 21 0:02 85 no 23.sz. 0:02 90 no No. 24 0:02 90 no 25.sz. 0:02 85 no 26.sz. 0:02 95 no 27.sz. 0:02 95 no Positive control 0:02 80 no untreated - 0 -

Note: Positive control: 50% benomyl wettable powder.

13. Experimental Example

Examination of tomato root knot nematodes

Soil infected with Meloidogyne incognita was mixed with 0.1 g of 10%. with the dust composition prepared according to Formulation Example 1. Powder compositions as active ingredient are 1-9, 20,

22, 24-27 containing compounds of the present invention. The mixture was placed in unpeeled pots of 12 cm diameter. Potted tomatoes (version: Ponté Rosa) were sown in pots, 15 seeds per pot! quantities. 15 to 50 days after soil treatment, tomato seedlings were removed from the pots and the phytotoxicity and puffer index determined by the following relationship:

gubac index = where A is the number of seedlings in which the roots have more than 31 cob,

B: the number of seedlings in which the roots were 21-30 cubes,

C: the number of seedlings in which the roots were 11-20 cubes,

D: The number of seedlings in which the roots were 1-10 cubes.

A goblet index, also known as a victory-clotting index, is a plant nematode, e.g. proportional to the number of nodules caused by infection with the Meloidogyne incognita nematode. The index expresses the severity of the infection of the root of the test plant by the nematode. The results are shown in Figure XIV. is shown in Table.

(4 x A) + (3 x B) + (2 x Cl + D

- _x 100 x (total number of seedlings) 60

-1 531

XIV. table

Test results of control of tomato root knot nematodes

Test compound Amount of compound per pot (g) gubácsin de x phytotoxicity E.g. 0:01 20 no No. 2 0:01 10 no No. 3 0:01 35 no No.4 0:01 60 no No. 5 0:01 55 no No.6 0:01 20 no No. 7 0:01 15 no 8.sz. 0:01 25 no 9.sz. 0:01 65 no No. 20 0:01 60 no 22.sz. 0:01 55 no 24.sz. 0:01 30 no 25.sz. 0:01 40 no 26.sz. 0:01 20 no 27.sz. 0:01 20 no untreated - 100 - 14. Experimental Example with the diluted emulsion prepared according to Example 1, which contains 20% of the total number of \ t Cucumber root knot nematodes 30 fractions, 200 ml per plant! quantity- examination of defense in. 40 days a after treatment with seedlings taken out of the soil and examined Soil infected with Meloidogyne incognite toxicity and calculations of puffer indexes. we transplanted cucumbers (version: fi green) (Experimental 13 example). The flies in 5 leaf condition. 10 days to 35 results for XV. shown in table after planting soaked the soil in Form 5 together. XV, table Cucumber knuckle knot nematodes test results of anti-fouling

Test compound Concentration of compound used (ppm) gall index phytotoxicity No. 2 125 14 no No. 2 250 16 no 2.sz 500 12 no untreated 100

Claims

PATIENT INDIVIDUAL POINTS

THE

X and Y are hydrogen or methyl;

separately = CH

1. Fungicidal and nematocidal compositions comprising: 0.595% by weight of N, N-disubstituted azole carboxamide derivatives of the formula (I):

k) is hydrogen, methyl, \ t

or nitrogen, with the proviso that when X is nitrogen, Y is nitrogen or = CH, and when X is = CH, Y is ethyl or propyl; C 1-6 alkyl

Z is an atom and is an oxygen or sulfur atom;

R8 is hydrogen or methyl; 65 with the proviso that when 7 is sulfur atom, A is hydrogen 17

-1633 and 5-99.5% excipients, including a carrier, preferably talc, clay or aromatic hydrocarbons, and optionally an emulsifier, preferably polyoxyethylene alkylphenyl ether or lauryl betaine; an additive, preferably carboxymethylcellulose or polyvinyl alcohol; a wetting agent, preferably polyoxyethylene-nonylphenyl ether; a tackifier, preferably a polyoxyethylene lauryl ether; disintegrant, preferably sodium lignin sulfonate and / or dispersant, preferably polyoxyethyl) alkylphenyl ether.

Previous: 1983.03.03.

2. Fungicidal compositions characterized in that the active ingredient is 0.5 to 95% by weight of the N, N-disubstituted azole carboxamide derivative of formula (Ia), wherein:

R1 is hydrogen, methyl or ethyl;

R 1 is C 1-6 alkyl;

X and Y are independently -CH- or nitrogen, with the proviso that when X is nitrogen, Y is N or = CH, and when X is = CH, Y is N and 5-99, 5% excipient, including a carrier, preferably talc, clay or aromatic hydrocarbons, and optionally emulsifying agent, preferably polyoxyethylene) alkylphenyl ether or lauryl betaine; a fastening agent, preferably carboxymethylcellulose or polyvinyl alcohol; a wetting agent, preferably polyoxyethylene-nonylphenyl ether; a tackifier, preferably a polyoxyethylene lauryl ether; disintegrant, preferably sodium lignin sulfonate and / or dispersant, preferably polyoxyethylene alkylphenyl ether.

Previous: 1982.03.04.

3. Nematocid formulations, characterized in that the active ingredient is 0.5 to 95% by weight of the Ν, ált-disubstituted azole carboxamide derivative of the formula (Ia), wherein:

R1 is hydrogen, methyl or ethyl;

R 2 is C 1-6 alkyl;

X and Y are each = CH or N, with the proviso that when X is N, Y is N or CH, and when X is CH, Y is N and 5-99, 5% excipient, including carrier, preferably talc, clay or aromatic hydrocarbons, and optionally emulsifying agent, preferably polyoxyethylene alkylphenyl ether or lauryl betaine; a fastening agent, preferably carboxymethylcellulose or polyvinyl alcohol; a wetting agent, preferably poly (oxyethyl) -nonylphenyl ether 18; a tackifier, preferably a polyoxyloxyeneuryl ether; disintegrant, preferably sodium lignin sulfonate and / or dispersant, preferably poi (oxyethylene) -a) phenylphenyl ether.

First place: 1982.07.30.

4. A fungicide and compositions comprising, as active ingredient, from 0.5 to 95 weight percent of compound (1b), wherein:

R1 is hydrogen, methyl or ethyl;

R1 is C1-C6 alkyl and Ra is hydrogen or methyl and 5-99.5% excipient, including carrier, preferably talc, clay or aromatic hydrocarbons, and optionally emulsifying agent, preferably polyoxyethylene alkylphenyl- ether or lauryl betaine; a fastening agent, preferably carboxymethylcellulose or polyvinyl alcohol; a wetting agent, preferably polyoxyethylene-nonylphenyl ether; a tackifier, preferably a polyoxyethylene lauryl ether; disintegrant, preferably sodium lignin sulphonate and / or dispersant, preferably polyoxyethylene alkylphenyl ether.

Previous: 1983.01.20.

5. The fungicidal composition according to claim 2, wherein the active ingredient is R 1 is methyl or ethyl, R 2 is C 1-6 alkyl, X is CH and Y is nitrogen.

Previous: 1982.03.04.

6. The fungicidal composition according to claim 2, wherein the active ingredient comprises (Ic), (id), (ie), (If), (Ig) or (1h). Previous: 1982.03.04.

The nematocidal composition according to claim 3, characterized in that it contains (le), (ld), (le), (If), (Ig) or (Ih). First place: 1982.07.30.

8. The fungicidal and nematocidal composition according to claim 1, wherein the active compound is III), (Ij) or (Ik).

Previous: 1983.03.03.

9. A process for the preparation of the N, N-disubstituted azole carboxamide derivatives of formula (I):

R1 is hydrogen, methyl, ethyl or propyl;

R2 is. C 1-6 alkyl;

R3 is hydrogen or methyl;

A is hydrogen or methyl;

X and Y sign, intrigue-on-CH-group

Or nitrogen, with the n-173o bond, when X is nitrogen, Y is N or = CH, and when X is = CH, Y is nitrogen and

Z is oxygen or sulfur, with the proviso that when Z is sulfur, A is hydrogen, characterized in that

a) a compound of formula (II) wherein R1, R2, Ra, A and Z are as defined herein, Hal is halogen with a compound of formula (III): wherein X and Y are as defined in the specification; or we react

b) reacting a compound of formula IV wherein X and Y are as defined above with a compound of formula V wherein R1, R2, R3, A and Z are as defined herein.

Previous: 1983.03.03.

10. A process for the preparation of compounds of formula (Ia): wherein R1 is hydrogen, methyl or ethyl;

R 2 is C 1-6 alkyl;

X and Y are each = CH or nitrogen, with the proviso that when X is nitrogen, Y is nitrogen or = CH, and when X is = CH, Y is nitrogen, characterized in that The compound of formula (IIa) wherein R1 and R2 are as defined in the general formula Hal is halogen with a compound of formula III wherein X and Y are as defined herein.

Previous: 1982.03.04.

Ii. A process for the preparation of compounds of formula (Ia): wherein R1 is hydrogen, methyl or ethyl;

R 2 is C 1-6 alkyl;

X and Y are each = CH or nitrogen, with the proviso that when X is nit10, Y is nitrogen or = CH, and when X is CH, Y is nitrogen, characterized by by reacting a compound of formula (IV): wherein X and Y are as defined above with a compound of formula Va in the following formulas: Ei and R2 are as defined herein.

Previous: 1982.03.04.

L2. Process for the Preparation of Compounds of Formula (db): wherein R1 is hydrogen, methyl or ethyl;

R 2 is C 1-6 alkyl and

R3 is hydrogen or methyl -, wherein the formula (IIb) generally ³ θ compound nos formula: - wherein Rl, R2 and R) is a halogen atom is as defined above and Hal - is reacted with (IIIa) Compound.

Priority: 1983.01.20,

13. A process for the preparation of compounds of formula (Ib): wherein: is hydrogen, methyl or ethyl; is a C1-C6 alkyl group and is hydrogen or methyl, wherein the compound of formula IVa is reacted with a compound of formula (Vb) wherein R1, R2 and R3 are as defined herein.

Previous: 1983.01.20.

rl

R2

R3 drawing

The Director of Economic and Legal Publishing is responsible for publishing

88,784.66-4 Alföldi Printing House Debrecen - Responsible manager: István Benkő CEO

-18190582

International Classification: A 01 N 47/38 A 01 N 43/50 A 01 N 43/653 A 01 N 43/06 A 01 N 43/56 C 07 D 231/12 C 07 D 233/56 C 07 D 249 / 08 C 07 D 307/52 C 07 D 333/22 (I) r ₂ ooc-hc (II)

Ri (III) (IV)

-19190582

International classification: A 01 N 47/38 A 01 N 43/50 A sitting N 43/653 A 01 N 43/06 A 01 N 43/56 C 07 D 231/12 C 07 D 233/56 C 07 D 249 / 08 C 07 D 307/52 C 07 D 333/22

C0 (Hal) ₂ (VI) (Hal) ₃ C-O-C-Hal (VII)

Hal — CH — COORd

RCH-NH ₂ (IX)

-20190582

International classification:

A 01 N 47/38 A 01 N 43/50 A 01 N 43/653 A 01 N 43/06 A 01 N 43/56 C 07 D 231/12 C 07 D 233/56 C 07 D 249/08 C 07 D 307/52 C 07 D 333/22

II

N-C-N / h ₂ h ^x

A) zCOOR ² (la) (lb)

N-

II

H-COOCH3 »3 (Ic)

II

N-C -

CH-COOC2H5 ch ₃ (ld) ch ₂

CH-COOCH (CH3) ₂ CHd (le)

-21190582

International classification: A 01 N 4 7/38 A 01 N 43/50 A 01 N 43/653 A 01 N 43/06 A N 43/56 C 07 D 231/12 C 07 D 233/56 C 07 D 249 / 08 C 07 D 307/52 C 07 D 333/22

CH2 xax · (H) ch-cooch3 c ₂ h ₅ (Ig)

TH-COOC2H5

C ₂ H ₅

Β c — Νς ⁰

XH-COOCHYCHPi c ₂ h ₅ (I h) (ii)

clj)

CH-COOCsHntizo)

CH3

-22CL '0' tx

NH

R ¹ 0 C -HC ^Z I

International Division & Volume: A 01 N 47/38 A 01 N 43/50 A 01 N 43/653 A 01 N 43/06 A 01 N 43/56 C 07 D 231/12 C 07 D 233/56 C 07 D 249/08 C 07 D 307/52 C 07 D 333/22 | = IN IN Οdl ch ₂ r ² ooc-h (p.)

CH-COOC ₆ H ₁₃ (n)

H ₃

II r

I1

N-C-Hal

1 H (Illa) (Ha) (II b) (IVa) (Vb) r (Va)

-23190582

International Classification: A 01 N 47/38 A 01 N 43/50 A 01 N 43/653 A 01 N 43/06 A 01 N 43/56 C 07 D 231/12 C 07 D 233/56 C 07 D 249 / 08 C 07 D 307/52 C 07 D 333/22 Rinse soak with dirt

CCZE

-O / 0 = 0

TENDON

CC o

o o

± / o

> cc <

cc — o o cc — O CO

0 = 0 σ

ZE

0 = 0